WO2007046377A1 - Method for producing melt-moldable fluororesin - Google Patents

Method for producing melt-moldable fluororesin

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Publication number
WO2007046377A1
WO2007046377A1 PCT/JP2006/320654 JP2006320654W WO2007046377A1 WO 2007046377 A1 WO2007046377 A1 WO 2007046377A1 JP 2006320654 W JP2006320654 W JP 2006320654W WO 2007046377 A1 WO2007046377 A1 WO 2007046377A1
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WO
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Application
Patent type
Prior art keywords
cf
ethylene
melt
copolymer
fluororesin
Prior art date
Application number
PCT/JP2006/320654
Other languages
French (fr)
Japanese (ja)
Inventor
Atsushi Funaki
Hiroki Kamiya
Original Assignee
Asahi Glass Company, Limited
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Family has litigation

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18Monomers containing fluorine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18Monomers containing fluorine
    • C08F14/26Tetrafluoroethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18Monomers containing fluorine

Abstract

Disclosed is a method for producing a melt-moldable fluororesin which enables to increase the molecular weight of the fluororesin while preventing coloration of the fluororesin by using a specific fluorine-containing emulsifier other than ammonium perfluorooctanoate. Specifically disclosed is a method for producing a melt-moldable fluororesin wherein a fluorine-containing monomer is emulsion-polymerized in an aqueous medium containing a fluorine-containing emulsifier represented by the following general formula (1). XCF2CF2(O)mCF2CF2OCF2COOA (1) (In the formula, X represents a hydrogen atom or a fluorine atom; A represents a hydrogen atom, an alkali metal or NH4; and m represents an integer of 0-1.)

Description

Specification

The method of producing a melt-moldable fluororesin

Technical field

[0001] The present invention relates to a manufacturing how the melt-moldable fluororesin using a specific fluorinated emulsifier.

BACKGROUND

[0002] In the production of a melt-moldable fluororesin by emulsion polymerization, emulsifiers as Pafuruo port octoate Anmoniumu used (hereinafter, referred to. APFO) is widely.

However, APFO is pointed out bioaccumulation, the discharge of APFO has been expressed concerns with environmental alternative to emulsifiers APFO has been required.

Therefore, in an aqueous medium by using various emulsifiers other than APFO, a fluorine-containing monomer alone or a fluorinated monomer and other monomers are copolymerized, it is proposed a method for producing a melt-moldable fluororesin are (e.g., see Patent documents 1 and 2). In the emulsion polymerization method of Patent Document 1, reduction in molecular weight of the resulting fluorine resin, coloration of the fluorine 榭 fat, applicability to the manufacture of a melt-moldable fluororesin was not so necessarily high enough.

The Examples of Patent Document 2, for the preparation of polytetramethylene Furuoroechiren modified with hexa full O b propylene to the very small amount, CF CF OCF CF OCF COONH as for emulsion polymerization

3 2 2 2 The use of 2 are disclosed, it is described about the application to the melt moldability fluororesin

Four

Les,.

The Examples of Patent Document 3, CF CF OCF (CF) CF OCF (CF as for emulsion polymerization

3 2 3 2

) COONH but are disclosed, the emulsifier bioaccumulation is to be higher than APFO

3 4

all right.

The Examples of Patent Document 4, F (CF) OCF (CF) COONH such as for emulsion polymerization

2 5 3 4 is disclosed.

Patent Document 1: JP 2002- 308913 JP

Patent Document 2: JP-B 39- 24263 JP Patent Document 3: JP 2003- 119204 JP

Patent Document 4: JP 2002- 317003 JP

Disclosure of the Invention

Problems that the Invention is to you'll solve

[0003] An object of the present invention, by using a specific fluorinated emulsifier other than APFO, it is possible to increase the molecular weight of the fluorine resin, melt-moldable fluororesin which can prevent coloring of the fluororesin to provide a method of manufacturing.

Means for Solving the Problems

[0004] The present inventors have found, as a result of intensive studies in order to solve the above problems, by emulsion polymerization of a fluoromonomer by using a specific fluorinated emulsifier, which is the table in the general formula (1), the can solve the problem, was Itaritsu completed the present invention based on the findings.

That is, the present invention has the subject matter characterized by the following.

(1) In formula (1): XCF CF (O) CF CF OCF COOA

2 2 m 2 2 2

(Wherein, X represents a hydrogen atom or a fluorine atom, A is a hydrogen atom, an alkali metal or NH

4 there, m is an integer of 0 :!. In an aqueous medium containing a fluorinated emulsifier represented by), the production method of the melt-moldable fluororesin, which comprises emulsion polymerization of fluorinated monomers.

[0005] (2) the fluorine-containing monomer, tetrafurfuryl O b, vinylidene fluoride, to Kisafu Ruo b propylene, in CF = CFOR (wherein, R is also an etheric oxygen atom

2 ff

There carbon number 1 to 16 which is par full O b alkyl group. ) Represented by Pafuruoro (Al kill Bulle ether), black hole triflumizole Ruo Russia ethylene, polyfurfuryl O b alkyl ethylene, Pafuruoro (2, 2-dimethyl _ 1, 3-Jiokisoru), Pafuruoro (4-alkyl-1, 3 during _ Jiokinoru) and CF = CF_〇 (CF) CF = CF (wherein, n is 1 or 2

2 2 n 2

is there. Method for producing a melt-moldable fluororesin according to (1) is at least one selected from the group consisting of).

[0006] (3) the melt-moldable fluororesin, tetrafurfuryl O b, vinylidene fluoride, to hexa full O b propylene and black port triflumizole Ruo Russia one even without less selected from the group consisting of ethylene method for producing a melt-moldable fluororesin according to (1) is a copolymer of a fluorine-containing monomer and ethylene.

[0007] (4) the melt-moldable fluororesin, tetrafurfuryl O b ethylene / Pafuruoro (§ Honoré Kino Levi Nino les ether Honoré) copolymer, tetra unloading Reo b ethylene / to Kisafunoreo port propylene emissions copolymer, tetrafluoropropoxy O b ethylene Z ethylene copolymer, tetrafurfuryl O b ethylene / to hexa full O b propylene z vinylidene fluoride copolymer, tetrafurfuryl O b ethylene z to hexa full O b propylene z ethylene copolymer, tetra Furuoroechiren / to Kisafuruo port propylene z Pafuruoro (alkyl Bulle ether) copolymer, available molten molding according to polyvinylidene Biniri den or black port triflate Ruo b / ethylene copolymer in the above (1) method for producing a fluorine-containing resin.

(5) 0.5 The content of the fluorinated emulsifier in the aqueous medium 01 to: (1 a 10 wt%

) Les to (4), the manufacturing method of the melt-moldable fluororesin according to any misalignment.

(6) The fluorine-containing emulsified Hitoshi IJ represented by the general formula (1) is, CF CF OCF CF OCF COO

3 2 2 2 2

Preparation of a melt-moldable fluororesin according to any one of the NH and the above (1) to (4)

Four

To provide a method.

Effect of the invention

According to the production method of the [0008] present invention, a high molecular weight Nag the APFO with concern that adversely affect the environment and Mochiiruko, melt-moldable fluororesin can be produced. Further, the fluorinated emulsifier adhered to the obtained fluororesin can easily removed by washing with water, if the obtained fluororesin was molded article, it is possible to prevent coloring.

BEST MODE FOR CARRYING OUT THE INVENTION

Fluorinated emulsifier used in the [0009] present invention is a fluorine-containing emulsifier represented by the formula (1).

Formula (1) XCF CF (O) CF CF OCF COOA

2 2 m 2 2 2

(Wherein, X represents a hydrogen atom or a fluorine atom, A is a hydrogen atom, an alkali metal or NH

4 there, m is an integer of 0 :!. )

[0010] In the general formula (1), X is preferably from the viewpoint of the stability of polymerization is a fluorine atom. Also, the value of m is preferred because it is one of the mechanical stability of the stability and the aqueous PTFE emulsion polymerization.

Specific examples of A, H, Li, Na, kappa, especially the force ΝΗ etc., in the case of ΝΗ is

4 4 solubility in water it is preferable Nag that Yogu metal ion component will remain as impurities in the fluorine resin.

Particularly preferred examples of the fluorinated emulsifier of the general formula (1) may, CF CF CF CF OCF CO

3 2 2 2 2

ONH, CF CF OCF CF OCF COONH (hereinafter referred to as EEA.) And is, EEA Gayo

4 3 2 2 2 2 4

Ri preferred.

[0011] The fluorinated emulsifier of the general formula (1), the liquid phase fluorination method to the corresponding esters of non-fluorine-containing carboxylic acid or partially fluorinated carboxylic acid is reacted with fluorine in Yore ,, liquid phase, fluoride it can be fluorinated by a known fluorination method of fluorination method or electrochemical fluorination method, such as using a cobalt, hydrolyzing the resulting fluorinated ester bond, obtained by neutralization with ammonia § after purification .

In the production method of the present invention, in an aqueous medium which contains the fluorinated emulsifier, and emulsion polymerization of a fluorine-containing monomer, an aqueous emulsion of a melt-moldable fluororesin is obtained, et al.

Content in the aqueous medium of the fluorinated emulsifier of the general formula (1) is rather preferably the aqueous medium is 0.01 to 10.0 mass 0/0, more preferably 0.:!~ 5 it is the mass%, and most preferably 2 to 3 wt% 0.1.

The [0012] aqueous medium, ion exchanged water, pure water, and a water such as ultrapure water. The aqueous medium may contain a water-soluble organic solvent. As the organic solvent, alcohols, ketones, ethers, ethylene glycol, propylene glycol and the like. The content of the organic solvent, is preferably tool 3 to 20 parts by force Beam preferably 1 to 50 parts by weight per 100 parts by weight of water. Note that the amount of aqueous medium as a reference for the content of the fluorinated emulsifier, does not include the content of other additives such as heavy initiator.

[0013] The fluorine-containing monomer used in the present invention, tetrafurfuryl O b ethylene, fluorinated vinyl alkylidene, to hexa full O b propylene, in CF = CF_〇_R (wherein, R, etheric oxygen

2 ff

Contain atoms which may the number of carbon atoms 1 to 16 which is par full O b alkyl group. ) Represented by Pas one Furuoro (alkyl Bulle ether), black hole triflumizole Ruo Russia ethylene, Porifuruoroaru kill ethylene, Pafuruoro (2, 2-dimethyl-1, 3-Jiokisoru), Pafuruoro (4-alkyl - 1, 3- Jiokisoru ) and CF = CFO (CF) CF = CF (in wherein, n

2 2 n 2 is 1 or 2. ) At least one is preferably selected from the group consisting of.

[0014] R as also may the number of carbon atoms 1 to contain an etheric oxygen atom: 10 Pafuruoroa f

Alkyl group is preferred instrument par full C1-8 O b alkyl group is more preferable les. Pfaff Ruoroarukiru group can be linear, branched, it may be any of circular. ί or as its specific examples, CF, CF, CF CF CF, (CF) CFCF CF, CF CF OCF CF, CF C

3 2 5 3 2 2 3 2 2 2 3 2 2 2 3

F CF OCF (CF) CF, and the like.

2 2 3 2

[0015] In the production method of the present invention, in addition to the fluorine-containing monomer further ethylene, flop propylene, it is also preferable to copolymerize Orefin of butene. As the Orefuin, preferably ethylene. The Orefuin is tetrafurfuryl O b, vinylidene fluoride, to hexa full O b propylene and black port triflumizole Ruo Russia ethylene force consisting of at least one copolymerizable it is preferable to implement selected from the group tetrafluoropropoxy O b Ethylene and at least one copolymerizable more preferably to Le selected from the group consisting of Kurorotorifu Ruoroechiren,

The amount of all monomers, relative to the amount of the aqueous medium, 1: and more preferably 100% by weight preferably fixture 10-80 wt%.

[0016] As the polymerization initiator used in emulsion polymerization, it is possible to use an ordinary radical polymerization initiator, Shi particularly preferred water-soluble polymerization initiator les. Specific examples of the water-soluble polymerization initiator, persulfate such as persulfate Anmoniumu salts, hydrogen peroxide and sodium hydrogen sulfite these, redox polymerization initiator comprising a combination of a reducing agent such as Chio sodium sulfate, further these small amount of iron, ferrous salt (such as ferrous sulfate), an inorganic polymerization initiator systems coexist and silver sulfate, or disuccinic acid peroxide, § zone bis isobutyl amidine dihydrochloride it can be exemplified an organic polymerization initiators such as salts.

The polymerization initiator may be added from the beginning of the emulsion polymerization, it may also be added Caro from the middle of the emulsion polymerization,.添Ka 卩量 of polymerization initiator, based on the total weight of the monomers used in the polymerization, 0.0 00:! ~ 3% by weight preferably tool 0.00: to 1 mass% is particularly preferred.

[0017] In order to adjust the pH of the aqueous medium in a range not to impair redox reactivity when using a redox polymerization initiator, it is preferable to use a pH buffering agent. The pH buffering agent,-phosphate disodium hydrogen, sodium dihydrogen phosphate, can Rukoto force S with inorganic salts such as sodium carbonate, disodium hydrogenphosphate dihydrate, disodium hydrogen phosphate 12 Water hydrate is good Masui.

Also, when using Redottasu polymerization initiator, as the metal ion redox reactions it is possible to use various metals having multiple ionic valences. Specific examples include iron, copper, manganese, transition metals preferred instrument, especially iron, such as chromium are preferred.

[0018] Furthermore, the metal redox reactions in order to exist stably in the aqueous medium, it is preferable to use a metal chelating one preparative agents. The metal chelating agent, Echirenjiamin tetraacetate compound is more preferably Echirenjiamin tetraacetate disodium dihydrate in view of Konomashigu soluble les.

The redox reaction reagent in the case of using the redox polymerization initiator, it is preferable to use a reducing compound. The reducing compound, various possible Rukoto force S with sulfuric sulfur-containing compounds, in particular Rongalite (chemical formula: CH (OH) SO Na '2H_〇) are preferred.

2 2 2

Reducing compound, it is preferable to adjust the same pH as the polymerization medium in order to be properly added continuously during the polymerization not to disturb the pH of Polymerization medium when the preferred tool added.

[0019] In the polymerization of fluorine-containing monomers may be used a chain transfer agent to control the molecular weight.

The chain transfer agent, methanol, and alcohols such as ethanol and propanol, 1,3 Jikuroro 1,1,2,2,3 pen tough Honoré Olof. Loja. Emissions, 1, 1 Jikuroro 1 Funoreo port ethanone down like a black hole Furuorohaido port carbon, methane, Etan, Purono emissions, butane, pentane, hexane, Hyde port carbon or the like cyclohexane and the like cycloheteroalkyl and the like to.

The addition amount of the chain transfer agent, based on the total weight of the monomers used in the polymerization, from 0.001 to 10% by weight preferably fitting 0. 01: and more preferably 10% by mass.

[0020] the emulsion polymerization conditions in the present invention, the type of monomer used, the copolymerization ratio is appropriately selected depending on the decomposition temperature of the polymerization opening initiator.

The polymerization temperature of the emulsion polymerization, 0: and more preferably 100 ° C is preferred instrument 10 to 80 ° C. The polymerization pressure is 0. 01~20MPaG force preferably, 0. 3~:! OMPaG is most preferred more preferred instrument 0. 3~5MPaG. Further, in the emulsion polymerization, batch, semi-batch, semi-batch, which form a continuous type or the like is continuously added the force monomer one used is either that the composition of the resulting fluorine resin is uniform et al, preferable. The concentration of the fluororesin in the aqueous emulsion to be obtained is rather preferably 1 to 50 wt%, more preferably 5 to 40 mass%.

[0021] in an aqueous emulsion of fluorocarbon resin obtained by the production method of the present invention, by adding an aggregating agent, it is possible to agglutinate fluororesin. It is also possible to agglutination by freezing the fluororesin aqueous emulsion.

Examples of the aggregating agent, any one force that is normally used for coagulation of the aqueous emulsion of fluorocarbon resin using an emulsifier such as APFO be used. For example, calcium chloride, mug chloride Neshiumu, Shioi匕 aluminum, water-soluble salts such as aluminum nitrate, nitric acid, hydrochloric acid, which acids sulfuric acid, alcohol, water-soluble organic liquid such as acetone. The addition amount of the aggregating agent with respect to 100 parts by mass of the fluororesin aqueous emulsion, 0.00:! ~ 20 parts by weight preferably fitting 0. 01: 10 parts by weight is particularly preferred. The concentration of the fluororesin in the aqueous emulsion liquid to be used for aggregation,:! ~ 50% by weight preferably tool 5 to 40 mass% is more preferable.

[0022] aggregated fluororesin is mouth specific, it is preferably washed with washing water. Is a washing water, ion exchange water, pure water, such as ultra pure water. The amount of washing water, the mass of the fluororesin 1: 10 times are preferable. Even with such small amounts, adhering to the fluororesin, the fluorinated emulsifier represented by the above general formula (1) can be sufficiently reduced by one washing. The number of washing, so little work of the preferred from the viewpoint tool 5 times less than the preferred tool:! ~ 3 times is more preferable. Washing temperature is usually 10 to 40 ° C are preferred.

[0023] contained in the waste liquid after being aggregated fluororesin aqueous emulsion obtained by the production method of the present invention, the fluorinated emulsifier represented by the above general formula (1) is recovered by known methods, can for re-禾 IJ. The recovery method, a method of adsorbing the strongly basic Anion exchange resin or a weakly basic Anion exchange resin, a method of adsorbing the synthetic adsorbent, how is adsorbed on activated carbon, a method for encapsulating the layered double hydroxide, the waste water how such as concentration and the like. Further, the fluorinated emulsifier recovered by the above method can be regenerated by a known method.

[0024] Specific examples of the melt-moldable fluororesin, tetrafurfuryl O b Ethylene Z to Kisafu Ruo b propylene copolymer (hereinafter, FEP Tomore, earthenware pots.), Tetrafurfuryl O b ethylene / perf Ruoro (propyl Bulle ether) copolymer (hereinafter also referred to as PFA.), Tetorafuruoroe styrene / ethylene copolymer (hereinafter, also referred to as ETFE.), polyvinylidene fluoride (hereinafter, also referred to as P VDF.), black hole triflumizole Ruo b ethylene / ethylene copolymer (hereinafter, also ECTFE les, earthenware pots.), tetrafurfuryl O b ethylene / to hexa full O b propylene / vinylidene fluoride copolymer polymer (hereinafter also referred to as THV.), tetrafurfuryl O b ethylene Z to Kisa full O b propylene / ethylene copolymer (hereinafter, EFEP Tomore, earthenware pots.), tetrafurfuryl O b Kisafuruo port propylene Z Pafuruoro (alkyl to ethylene Z Yurueteru) copolymer (hereinafter, intends Rere both EPA.), Polyvinylidene fluoride (hereinafter, also referred to as PVDF.), Black hole triflumizole Ruo Russia ethylene Z E styrene copolymer (hereinafter, ECTFE Tomore, earthenware pots.) Is and the like.

[0025] The composition of the FEP, tetrafurfuryl O b to ethylene Z hexa full O b molar ratio power s 97/3 to 80/20 Power preferably propylene, more preferably from 95/5 to 90/10. The composition of PFA, the molar ratio of tetrafluoropropoxy O b Ethylene Z Pafuruoro (propyl Bulle ether Honoré) is 99. 9/0:.!. ~ 95/5 force S Preferably, more preferably 99. 7/0 3-97 / 3. The composition of the ETFE, tetrafurfuryl O b ethylene / ethylene molar ratio is rather preferably 70 / 30-40 / 60, more preferably from 65 / 35-50 / 50. The composition of THV, the tetrafurfuryl O Roe Chile on / to hexa full O b propylene / molar ratio forces of vinylidene fluoride S25~85 / 5~15 / 10 ~60 force S Preferably, more preferably 35 to 75/5 it is a 15/20 to 50.

[0026] The composition of EFEP, the tetrafurfuryl O b ethylene / to hexa full O b propylene / ethylene Monore]; 匕力 20-75 / 5-20 / 20-60 force S Preferably, more preferably ί or 35-65 / 5 to 15 / 30-50. The composition of ΕΡΑ is tetrafurfuryl O b ethylene / to hexa full O Ropuro Pile on / Pafuruoro molar ratio power ¾2~96 · 9 / 3~ of (alkyl Biel ether Honoré): 15/0:.! ~ 3 Power Preferably, more preferably a 88 to 94.8 / 5-10 / 0.2 to 2. The composition of ECTFE, the molar ratio of black hole triflate Ruo Russia ethylene Z ethylene lay preferred is 70Z30~40 / 60, more preferably from 65 / 35-50 / 50.

[0027] As a measure of the molecular weight of the melt-moldable fluororesin, are used in MFR (melt flow rate) gar 2.20. As MFR is small, indicating that the molecular weight is large. Temperature measured MFR is above the melting point, but can be measured at a temperature below the decomposition point, a constant temperature is generally used depending on the type of fluororesin. For example, PFA, FEP, EPA in 372 ° C, ETFE, EC TFE in 297 ° C, THV in 265 ° C, EFEP in 230 ° C, PVDF in 235 ° C is usually used. A preferred range of MFR is 0 - 1: at OOG / min, more preferably 0. 5 to 50 g / min, and most preferably: a ~ 30 g / min.

Tensile strength at room temperature of the molten moldable fluororesin is more LOMPa, preferably 15 MPa or more, most preferably 20 MPa, room temperature tensile elongation of 100% or more, preferably rather is 150% or more, most preferably 200% or more.

Example

[0028] Next, description in more detail of the present invention through examples, but these are not shall be construed as limiting the present invention.

The evaluation method of each item are shown below.

[PFA of the composition analysis]

PFA was used a film of press molding thickness was prepared by 30 mu m. The absorbance at 993cm _ 1 as measured by infrared spectrometer analysis, divided by the absorbance at 2350 cm _ 1, as a value multiplied by 0.95, the content of Polymerization units based of Pafuruoro in PFA (propyl Biel ether) ( to determine the mass%).

[0029] [FEP of the composition analysis]

FEP was used a film of press molding thickness was prepared by 30 mu m. The absorbance at Shitaderutaomikuron'omikuronpai 1 as measured by infrared spectrometer, divided by absorbance at SSSOcnT 1, 3. As multiplied digit value 2, the content of F hexa full O b propylene with based polymerized units in FEP (mass%) I was determined.

[ETFE of the composition analysis]

Was determined copolymerization composition of ETFE by 19 F melt NMR analysis and fluorine content analysis.

[0030] [MFR (Unit: gZ minute) measurement of]

In conformity with ASTM D2116, using a melt indexer (manufactured by Takara Kogyo Co., Ltd.) to measure the MFR (also referred to as capacity flow rates.). PFA, in the case of FEP was measured at 372 ° C, load 5 kg. For E TFE was measured at 297 ° C, load 5 kg. In the case of PVDF was boss measured at 235 ° C, load 5kg.

[0031] g of Reference Example 1 CF CF OCF (CF) CF OCF (CF) COONH of preparation volume 200ml Hasuteroi C autoclave to a 2 · 58 g and tetraglyme of CsF 13.06 g of degassed this after, it was introduced 20 · 83g of CF COF. Then, 該O

3

After cooling an Tokurebu to 20 ° C, sealed under stirring, hexa full O b propene O carboxymethyl were introduced 57.5g of de over about 1 hour to. It showed the initial pressure 0.6MPa. Was continued for about 1 hour to reduce the pressure such Kunar to give 78.57g of crude reaction solution was returned to room temperature. This was GC analyzed, CF CF OCF an objective compound (CF) CF OCF (CF) C_〇_F 49.7% of

3 2 3 2 3

In addition to, CF CF_〇_CF (CF) 19.1% of the COF and CF CF 0 (CF (CF) CF O)

3 2 3 3 2 3 2 2

12.8% of CF (CF) COF has been included.

3

[0032] The same reaction was performed using 32.26g of CF COF. Containing the resulting target compound,

3

The distillation was carried out together 2 batches of the reaction crude liquid. With distillation column 30cm packed with reflux condenser and Helipack No.1, was obtained 52.47g of desired product boiling 71 ° CZ400torr. G of target product in a PTFE reactor was dropped hydrolyze the 2.32g of water with stirring. Then, row-de-HF by nitrogen bubbling ,, CF CF_〇_CF (CF) CF

3 2 3 2

To obtain a 50 · 45 g of the crude liquid OCF (CF) C_〇_OH. The glass single distillation apparatus the crude liquid

3

Simple distillation to obtain a 40g of CF CF OCF (CF) CF OCF (CF) COOH.

3 2 3 2 3

[0033] Then, using 40g of CF CF OCF (CF) CF OCF (CF) COOH Anmoniumu

3 2 3 2 3

Chloride were carried out. The glass reactor was dissolved 40g of Yore ,, the carboxylic acid to 150g of CC1F CF CHC1F, was then added dropwise to § Nmoniumu Shioi匕 the 10 · 89 g of 28% aqueous ammonia at room temperature thereto. Then, after distilling off the CC1F CF CHC1F solvent, the CF CF OCF (CF) CF OCF (CF) C_〇_ONH more 39.4g dried under reduced pressure to give a white solid

3 2 3 2 3 4

[0034] Reference Example 2 1 Okutanoru measurement of Z water partition coefficient (LogPOW)

In compliance with OECD Test Guideline 117, using HPLC (high performance liquid chromatography), the fluorinated emulsifier was measured 1 Okutanoru Z water partition coefficient (LogPOW).

Measurement conditions Column: TOSOH Rei_03_120 chome column (4.6 mm X 250 mm), solvent syneresis: Asetonitoriru Ζθ.6 wt% HC1_rei solution = l / l (vol / vol%), flow rate: 1.0 m

1 / min, Sanpunore amount: 300 ^ L, column temperature: 40. C, the detection light: UV210nm, was (see public WO2005- 42593 when the country).

[0035] 1 Okutanoru / water partition coefficient is a known standard for (heptanoic acid, octanoic acid, nonanoic acid and decanoic acid), from Okutano Le / water partition coefficient of row-,, each elution time and the standard of the HPLC a calibration curve was prepared. Based on this calibration curve, the elution time of H PLC of the fluorinated emulsifier gave calculate the value of the partition coefficient (LogPOW) between 1-Okutanoru and water. The results are shown in Table 1.

EEA, since the value of LogPOW is small compared to the par full O b octoate Anmoniumu (APFO), it can be seen that a low bioaccumulation. On the other hand, CF C synthesized in Reference Example 1

3

F_〇_CF (CF) CF OCF (CF) COONH the force EEA and structure are similar S, the LogP

2 3 2 3 4

OW values ​​force S, the accumulation of the magnitude tool organisms than APF_〇 that bioaccumulation is concerned was found high Ikoto.

[0036] In general, chemicals in order to determine whether those les, which ease accumulated in the organism, measurement test method for the partition coefficient between 1 Okutanoru and water (LogPOW) is defined ing. As the test method, in addition to the OECD test guideline 107 and JIS Z 7260- 107 (2000) "Measurement flask shaking method of distribution coefficient (1 Okutanoru / water)", as specified in OECD Test Guideline 117, published and has HPLC method (high performance liquid chromatography method) is employed. The value of the partition coefficient is large compound bioaccumulation large appliances small compounds indicate that bioaccumulation is small. Is not a high bioconcentration when the value of LogPOW of 3.5 non-drop, and has is appropriate to determine, considered bioaccumulative also small.

[0037] [Table 1]

[Example 1] Production of PFA

1. equipped with a stirrer, was deaerated polymerization tank 3L, 600 g of ion-exchanged water was 溶力 the 3g of EEA, 1 · 0 g of methanol, CF = CF_〇_CF CF CF (Pafuruoro (propyl vinyl ether

2 2 2 3

Le), hereinafter referred to as PPVE. 35g of), and persulfate Anmoniumu salt (hereinafter, APS referred.) Were charged 0 · lg of the stirring rotational speed was stirred as 300i "pm. In the polymerization vessel was heated to 65 ° C, Tetorafuruoro ethylene (hereinafter, TFE referred.) were charged, as 1 · 0M Pa pressure inside the polymerization vessel, the polymerization was allowed to start. viewed continuously charged with TFE during the polymerization pressure is kept constant, the continuous charging of TFE the amount will cool the inside of the polymerization vessel to room temperature when it becomes 200 g, it was opened. polymerization tank unreacted TFE was purged and freeze the resulting aqueous emulsion, to precipitate a copolymer and destroy washing was repeated three times with deionized water 1000ml (25 ° C) after. then dried 12 hours at 0.99 ° C, was obtained TFEZPPVE copolymer 205g. the resulting et a copolymer , a melting point of 305 ° C, MFR is 15 g / min, a content of the polymerized units based on PPVE in the copolymer is 3.9 wt% (1.47 mol%), Was melt-moldable fluororesin. 340 was pressure pressed at ° C, a white sheet without coloration obtained. The thickness 1. were punched tensile test micro dumbbell from a sheet of 5 m m. Tensile strength there 28MPa, the argument ChoShindo was 400%.

[0039] EXAMPLE 2 Production of FEP

Was degassed same polymerization vessel as in Example 1, 600 g of ion-exchanged water was dissolved 3g of EEA, Kisafuroro propylene to charged 0. 3g of 200g and APS (hereinafter, referred to as HFP.), Stirred and stirring rotational speed as 300rpm did. The inside of the polymerization vessel was heated to 65 ° C, charged with TFE, and the pressure in the polymerization vessel 1. to initiate polymerization as 5 MPa. Charged TFE during the polymerization pressure became constant connection to communication, continuous charging of TFE is cooled to room temperature polymerization vessel as they become 150 g, and the unreacted monomers were purged. The polymerization tank was opened, by freezing the obtained aqueous emulsion, After precipitation of the fracture to the copolymer, was repeated three times washed with deionized water 1000ml (25 ° C). Then dried 12 hours at 150 ° C, TFE / HFP copolymer of 160g was obtained. The resulting copolymer has a melting point of 261 ° C, MFR is 17gZ content, the content of polymerized units based on HFP in the copolymer is 11.8 wt% (7.9 mol%), melt molding It was possible fluorine resin. Was pressure-pressed at 340 ° C, a white sheet without coloration was obtained. Thickness 1. were punching tensile test the micro dumbbell from a sheet of 5mm. Tensile strength degree of 25MPa, the tensile elongation was 380%.

[0040] EXAMPLE 3 Production of ETFE

It was degassed same polymerization vessel as in Example 1, 600 g of ion-exchanged water was dissolved 6g of EEA, tertiary Butanonore of 60 g, (per full O b butyl) ethylene (hereinafter, PFBE and Le, Cormorant.) Of 2 · 4g It was charged 0. 15 g of APS, were stirred with a stirrer rotational speed as 300 rpm. TFE of ll lg, E styrene was 8g was charged polymerization reactor to initiate the raising temperature polymerization 65 ° C (149 ° F) of (hereinafter. Referred E). The polymerization pressure was 2. 9 MPa. Charged monomer mixture of TFE / E = 53/47 molar ratio during the polymerization pressure is kept constant continuously, were charged PFBE of 0. 3 g each time charged monomer mixture 10g. Continuous feed of the monomer mixture is cooled to room temperature polymerization vessel as they become 270 g, and the unreacted monomers were purged. The polymerization tank was opened, by freezing the resulting aqueous emulsifying solution, After precipitation of the fracture to the copolymer, was repeated three times washed with deionized water 1000ml (25 .C). Then dried 12 hours at 150 ° C, TFEZ E copolymer 285g was obtained. The resulting copolymer has a melting point of 262 ° C, MFR is 8gZ amount such that the molar ratio of polymerized units based on polymerized units ZPFBE ​​based on polymerized units / E based on TFE in the co-polymer 52. 5/46. 7/0. a 8 was melt-moldable fluororesin. 300 was pressure pressed at ° C, a white sheet without coloration was obtained. I was punching tensile test the real black dumbbell from the sheet with a thickness of 1. 5mm. Tensile strength 32 MPa, tensile elongation was 320%.

EXAMPLE 4 Polymerization of PVDF

Was degassed same polymerization vessel as in Example 1, 600 g of ion-exchanged water was dissolved 3g of EEA, 1 of acetone. 2 g, APS of 0. 3g, vinylidene fluoride were charged 40g (hereinafter, referred to. VDF), stirred times were rolling number stirred as 300rpm. The inside of the polymerization vessel was initiated heated to polymerization 65 ° C. Polymerization pressure was 2. OMPa. The VDF during the polymerization pressure is kept constant to see charged continuously, continuous charge of VDF is cooled to room temperature polymerization vessel as they become 180 g, and the unreacted monomers were purged. The polymerization tank was opened, by freezing the obtained aqueous emulsion, After precipitation of the fracture to the copolymer, was repeated three times washed with deionized water 1000ml (25 ° C). Then dried 12 hours at 0.99 ° C, 170 g of PVDF were obtained. PVDF is, melting point 166 ° C, MFR is 3. a 2 g / min was melt-moldable fluororesin.

Caro pressure pressing at 300 ° C, a white sheet without coloration was obtained. I was punching tensile test the micro dumbbell from the sheet with a thickness of 1. 5mm. The tensile strength was 45MPa, the tensile elongation force ¾40%. Industrial Applicability

Melt-moldable fluororesin obtained by the production method of the present invention can be utilized in a variety of applications like the conventional fluororesin. Specific examples, wire coating, wire jackets, chemical solution or pure water tube, copy roll covers, fuel hoses, agricultural or structural materials, release films, such as extrusion of the valve, the pump housing, automotive parts, copy machine parts, semiconductor manufacturing devices injection-molded products such as components, it is powder molded product such as a tank lining like et be. Incidentally, Akira Itoda Manual October 2005 20 曰 in 曰本 patent application filed 2005- No. 305,659, claims, and by reference in their entireties abstract here, the disclosure of the specification of the present invention to, is intended to incorporate.

Claims

The scope of the claims
[1] General formula (1) XCF CF (O) CF CF OCF COOA
2 2 m 2 2 2
(Wherein, X represents a hydrogen atom or a fluorine atom, A is a hydrogen atom, an alkali metal or NH
4 there, m is an integer of 0 :!. In an aqueous medium containing a fluorinated emulsifier represented by), the production method of the melt-moldable fluororesin, which comprises emulsion polymerization of fluorinated monomers.
[2] The fluorine-containing monomer is, tetrafurfuryl O b ethylene, Kisafuruo port propylene vinylidene fluoride to, during CF = CF_〇_R (wherein, R, may coal also contain an etheric oxygen atom
2 ff
Prime 1: 16 is a Per full O b alkyl group. ) Represented by Pafuruoro (Arukirubi vinyl ether), black hole triflumizole Ruo Russia ethylene, polyfurfuryl O b alkyl ethylene, perforation Noreoro (2, 2-dimethyl-1, 3 Jiokisoru), Pafuruoro (4 alkyl 1, 3 - Jiokisoru) and CF = CFO (CF) CF = CF (wherein, n is 1 or 2.)
2 2 n 2
Method for producing a melt-moldable fluororesin of claim 1 is at least one selected from the force becomes the group.
[3] The melt-moldable fluororesin, tetrafurfuryl O b, vinylidene fluoride, to hexa full O b propylene and black port triflumizole Ruo Russia from small selected group consisting of ethylene Kutomo one fluoromonomer method for producing a melt-formed shape capable fluororesin according to claim 1 which is a copolymer of ethylene and.
[4] The melt-moldable fluororesin, tetrafurfuryl O b ethylene / Pafuruoro (alkylene Honoré Bulle ether Honoré) copolymer, hexa full O b propylene copolymer polymer to tetrafluoropropoxy O b ethylene Z, Tetorafuruoro ethylene Z ethylene copolymer, tetrafurfuryl O b key fully O b propylene z vinylidene fluoride copolymer to ethylene z, tetrafurfuryl O b ethylene / to hexa full O b propylene z ethylene copolymer, tetrafurfuryl O b ethylene / to Kisafuruoropu propylene / Pafuruoro (alkyl Bulle ether) copolymer, a method of manufacturing a melt-moldable fluororesin according to claim 1 which is polyvinylidene fluoride or chloride port triflate Ruo b / ethylene copolymer.
[5] 0. content of the fluorinated emulsifier in the aqueous medium 01: production method of melt-moldable fluororesin according to 10 wt% a is any of claims 1-4. Fluorinated emulsifier represented by the general formula (1) is, CF CF OCF CF OCF COONH
3 2 2 2 2 a method for producing a melt-moldable fluororesin according to any one of claims 1 to 4.
PCT/JP2006/320654 2005-10-20 2006-10-17 Method for producing melt-moldable fluororesin WO2007046377A1 (en)

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